Color developers for the production of azine dye images



Patented Oct. 2, 1951 COLOR DEVELOPERS FOR THE PRODUC- TION OF AZINE DYEIMAGES Robert C. Gunther, Easton, Pa., assignor toGeneral Aniline & FilmCorporation, New York, N; Y., a corporation of Delaware No Drawing.Application June 28, 1949, Serial No. 101,913

The present invention relates to the production of azine dye images bycolor forming development while employing as the color forming developerderivatives of ZA-diamino aniline in which the amino group in the2-position is substituted by an. aliphatically linked hydrophilic group.

This application. is. a continuation-in-part of my application SeriaLNo.793,532, filed December 23,. 1947,, now abandoned, entitled ColorDevelopers for the Production of Phenazonium Dye;- stufilmages.

Inthe copending application Serial No. 640,382, filed on January 10,1946, by Willy A. Schmidt and Vsevolod Tulagin, now U. S. P.. 2,486,440,there is described, the production of azine dye images by color formingdevelopment while utilizing inter alia as the color developerderivatives f, 2,4'-diamino-aniline. While these color developershavebeen found to be effective-inproducing the desired dyestuff images inthe presence of the usual color forming componentsit is noted that theyhave atendency tobe. adsorbed to silver halide. grains. of thephotographic emulsions, thereby making it difficult 110: efiectthecomplete removal thereof from the emulsion by washing after development.Furthermore, saidv compounds have been observed-to cause staininthereduction of silver halides, particularly when such. reduction takesplace in the absenceoi a color former.

Difiiculties have also been encountered in the production of yellow dyeimages by the utilization of the. aforestated developers. Experience hasshown that when using'such developers with color formers generallyemployed for the production of. yellow azomethine images, i. e., openchain;

keto methylene compounds, magenta images rather than yellow imagesensue. The emagenta: images may besubsequently converted-into yellowimages but only by a separate step involving a treatmentwith an alkali.

It has now been-discovered that the production of azine dye images canbe effectively carried out without the aforenotedobjectionsif there beemployed as color developers derivatives'of 2,4-diamino anilinesin whichthe amino group in the 2.-po'sition is; substituted. by an aliphaticallylinked hydrophilics group such: as; hydroxyj, car

boxy or sulfo. Inasmuch as said compounds are:

capableofi effecting the reduction of silver halides including; latentimages without the formation of 13 Claims. (Cl. 9588) stain, they mayalso be employed as developers for black and White images.

These developers also havethe unique property of yielding yellow dyeimages directly when employed to develop a developable silver halideemulsion in the presence of an open chain keto methylene compound. Theyare therefore admirably suited for the production in one developmentstep of azine dye images in the three subtractive colors.

Developers utilizing such compounds and their employment particularly inthe production of azine dye images constitutethe purposes and object ofthe present invention.

The derivative of 2,4-diamino aniline contemplated for use herein asdevelopers are typified by the following structural formula:

NR R

wherein R is hydrogen or alkyl, i. e., methyl, ethyl, propyl, butyl,amyl or the like and R1 is an aliphatic radical such as alkyl as above,carboxy alkyl, such as carboxy methyl, carboxy ethyl, and the like;hydroxy alkyl, such as hydroxy ethyl, hydroxypropyl, andthe like, aryl,such asphenyl, toluyl and the like; carboxy alkyl aryl, such as oarboxymethyl phenyl, carboxy ethyl phenyl, and the like, carboxy alkoxy aryl,such as carboxy methoxy phenyl, carboxy ethoxyphenyl; hydroxy alkylaryl, such as hydroxy methyl phenyl, hydroxy ethyl phenyl, and the like;and hydroxy alkoxy aryl, such as hydroxy. methoxy phenyl, hydroxy ethoxyphenyl and the like, R2 is an alkyl group substitutedby a hydrophilicgroup such as carboxy alkyl, such as carboxy methyl, carboxy ethyl andthe like; hydroxy alkyl, such as hydroxy ethyl, hydroxy propyl, and thelike; sulfo alkyl such as, sulfomethyl, sulfoethyl, sulfop-ropyl,sulfobutyl and the like and X and Y are hydrogen, alkyl as above, sulfoorcarboxy, or together represent the atoms necessary to complete asixmembered isocyclic ring system such as benzo and the like. It is tobe observed that in the above compounds the substituent groups repre-HNGO c1110 OH N-CHzCHaOH 4- (B-hydroxyethylamino -6- (4' -carbozzy-methoxy phenylamino) metamlic acid Nil-@OCHa 4-( carbpxymethylamino)-6- (4-methoxy phenylamino metanilic acid l qHz 2- (B-sulfoethylamino)-4-phenylamino aniline NH C Hz 0 H2 0 H NHCHQOHZOH 4, G-di(B-hydroxyethylamino )-metanilic acid 2- B-hydroxyethyiamino) 4-(B-sulfoethylamino) --methyl aniline HOzS NHCHr-HOH 4B-hydroxy-f:-methyl-ethylamino) -6-phenylaminometanilic acid 8 0 CaHsCHIOH 4- (a-di (hydroxymethyl ethylamino -6- (3'-ethoayphenylamino)-metanilic acid 9 NHCHI NHCHaCHaOH l THz 4- (B-hydroxyethylaniino) -6-methylamino-metanilic acid moms 03H4-(sulfomethylamino)-6-(metl1gl phenyl amino)-metanilic aci Theaforementioned compounds are prepared by reacting in the proper sequence2,4-dichloro- 5-nitro benzene sodium sulfonate with the amines desiredto be introduced into the 2- and 4-positions of the benzene ring, andthen effecting reduction of the nitro group to an amino group. Thepreparation of the compound by the aforesaid method is made possible bythe fact that the chlorine atom in the 4-position is more easilyreplaced by an amino group than the chlorine atom in 2-position. Thus byrefluxing the 2,4-dichloro-5-nitro benzene sodium sulfonate with anequivalent of an amine, the chlorine atom in 4- position is selectivelyreplaced by such amine. By subsequently treating the resulting compoundwith the same or a different amine under more elevated temperatures, i.e., temperature ranging from to 150 C., the chlorine atom in Z-positionis replaced by the amine.

The following is a specific illustration of the application of theforegoing general method in the production of l-(p-hydroxyethylamino)-6- phenyl amino metanilic acid.

Into a 1-liter, 3-necked round-bottom flask equipped with a mechanicalstirrer and a reflux condenser was placed 147 parts of the sodium saltof 2,4-dichloro-5-nitro benzene sulfonic acid, 31 parts of ethanolamineand 54 parts of sodium carbonate dissolved in 250 parts of water. Afterthe stirrer was started, the contents of the flask were gently refluxedfor 10 hours. 200 cc. of 30% sodium chloride solution were added to thehot reaction mixture and the flask was then cooled in an ice bath. Theprecipitated orange solid was collected by filtration, washed with asmall amount of water, and dried overnight at 80-90 C.

A glass interliner for an Aminco shaking-type bomb was charged with 95.6parts of the 2-chlorol-(p-hydroxyethylamino)-5 nitro benzene sodiumsulfonate (prepared as above), 30 parts of aniline and 34 parts ofsodium carbonate dissolved in 200 parts of water. The liner was sealedin the bomb and the bomb shaken at C. for 15 hours. The bomb was cooledand the solid removed from the interliner with small amounts of hotwater. .250 cc. of 30% sodium chloride solution were added with vigorousstirring of the mixture and the whole was then cooled in an ice bath forseveral hours. The precipitated solid was collected by filtration,washed with 50 parts of water, and then digested with 200 parts ofethanol. The product was again collected on a filter and dried overnightat 60 C. in a vacuum oven.

10 parts of 2-phenylamino-4-(fi-hydroxyethylamino) -5-nitro benzenesulfonic acid (prepared as above) were added portion-wise to a boilingsolution of 40 parts of sodium hydrosulfite in 200 cc. of sodiumhydroxide. After reduction is complete, a small amount of decolorizingcarbon is added to the solution. The mixture is boiled vigorously forseveral minutes and then filtered rapidly through a fluted filter.Thecompound was then isolated from the clear filtrate as the inner saltby acidification with glacial acetic acid. The mixture was cooled in anice bath for several hours, the inner salt collected on a filter andwashed with water. The product was then dried six hours at 65 C. in avacuum oven and constituted the 4-(B-hydroxyethylamino)-6-phenylamino-metanili'c acid.

The same procedure may also be utilized in the preparation of the othercompounds noted above while employing amines containing an aliphaticallybound hydrophilic group different from that described in the aboveexample. Such other amines are for instance B-sulfoethyl amine (taurine)m-amino-phenoxy-acetic acid, amino acetic acid, p-amino phenyl ethylalcohol, 10- amino phenyl acetic acid, 2-amino-2-methyl- LB-propanedioland the like.

As stated, the aforementioned derivatives of 2,4-diamino aniline arecharacterized by their marked ability to effect reduction of silverhalides, i. e., latent images, reverse images, bleached images, and thelike, without formation of ob-.

jectionable stain. As a consequence of the reducing power they may beemployed for development of black and white images or for the productionof color images.

One of the mst notable properties of the aforementioned derivatives of2,4-diamino aniline, however, is, as stated, their ability to directlyyield yellow dyeimages. This result is achieved when employin thedevelopers to develop a developable silver halide emulsion in thepresence of an open chain keto methylene compound even though theemulsion during a, subsequent processing step be treated with an acidicbleach bath as is usual in the processing of film to azine dye images.In other words, whereas the formerly employed, ZA-diamino anilines onlyyielded yellow images, as the result of a subsequent alkaline 6.consequence such developers very materially contribute to theutilization on a commercial scale of the azine method for processingfilm in the three subtractive colors.

The yellow dyes obtained by color development with my developers appearto be true azines. Thus "they withstand treatment with an acid bisulfitewhereas yellow azomethines do not. Furthermore they are not split bystrong mineral acids as happens with the yellow azomethines. Such yellowdye images have excellent lightfastness and brilliance and theyadequately complement the magenta and cyan dyes produced by the minemethods.

The color formers employed for producing the dye images are those usedin the production of color developed images, i. e., those containingaromatic-primary amino, phenolic hydroxyl or active methylene groups.

Examples of such compounds for producing the magenta images are:3.6-d-isulfo-8-benzsulfonylamino naphthol-1;8-benzsulfonylaminonaphthol-1; B-hydroxy quinoline; naphthsultam acid;3-sulfo-7-phenylaminonaphthol-l; li8- bi's- (benzsulfonylamino)-naphthalene; 6-bromo-8- hydroxy quinoline; 6-sulfo-8-hydroxyquinoline;

Z-phenyl-6-bromo-8-hydroxy cinchoninic acid; 6-bromo-8-hydroxyquinaldine; G-stearoylamino 2 (2-phenyl-6'-bromo-8-hydroxy cinchoninoyl)-amino to'luene-4-sulfonic acid; 2-phenyl- G-chloro-S-hydroxycinchoninoyl octadecyl taurine, and the like.

Examples of cyan color formers are: 3-sulfo- 6 aminonaphthol 1; 3sulfo-S-phenyl-aminonaphthol 1; 3-sulfo-6-(4-methoxy-phenylami no)-naphthol-l; ethyl urethane of phenyl J acid; 6 (4'octadecoxy-phenylamino) -1-naphthol-B-sulfonic acid;3-sulfo-6-oleylamino-naphthol-l, and the like.

are:

j 4. N,N'-ethylenebisacetoacetamide CHaCOCHzCO NH' CH2CH2NHCOCH2COCH3 5.N .N '-ethylenebis-a-benzoylacetamide. 6. p.p'-Bi-o-acetoacetanisideQQNHGOGmOO 0H.

CHsO O CHzC ONH I a '7. N-2-naphthylbenzoylacetamide. 8.p.p-Biacetoacetanilide.

9. p.p-Bi-a-benzoylacetanilide.

10. and 'I'erephthaloylbis-(3chloro-4.6dimethoxy-acetanilide) treatment,the developers contemplated herein yield such images directly andWithout such subon, OlQNH-C o c1120 oQ-co-omc OHN sequent processingwith an alkaline bath. As a,

11. a4! Terephthaloylbis (4-chloro-5-methylo-acetaniside) on. p

12. a-Benzoylacetanilide.

Examples of yellow color forming components 7 8 13. 12(m-benzoylacetamidophenyl) -1-octadecy1- 33.'pCyanoacetyl-3-octadecenylsuccinialic acid. "5-benzimidazolesulionicacid. COOECN 14. o-Acetoacetaniside. v OH ZOOoH V V 15.4.4"-methylenebis-a-benzoylacetanilide. The processor employing thecolor developer QO0GHzCONHC CHz--ONHOOCH}Q 00' a l oPhenylacetoacetanilide. to produce the azine 'dye images may be effectedin 17.. 4'-2-pyridylsulfamyl-a-benzoylacetanilide. various ways. Forinstance, a color formingcom- 1 V ponent may. be added to the developercontaining the 5 diamino aniline derivative. On the other hand; a colorformer in non-diffusing form may be C COCHNH SOzNH located in theemulsion and the diamino aniline N derivative in the developer.Multi-layer film, 18. 5.5'-ureylenebis-N-benzoylacetyl anthranilic eachlayer containing a non-diffusing color acid. former, may be used and theentire film color OOOCHzOONH-O-NHCONHQNHCOClEizCO eoon (300E V r g 19.3.3 -ureylenebis 6 p benzoylacetamidodeveloped to. the desiredsubtractive dyestufi benzamide-benzene sulfonic acid. images in a singlecolor forming development step using the diamino aniline derivatives asthe de- -oooH2 o ONHOOONHQ I veloperu. V V

S0311 NH While the diamino aniline derivative and an 3 alkali, such assodium carbonate, sodium hydroxllIH ide, or the like, are the essentialcomponents of the developer, it is .preferred that the developer alsocontain the usual adjuncts such as an alkali metal bromide, i. e.,.potassium bromide, sodium bromide, and the like, and an alkali metalsulfite,

O0 0 011,0 ONE-O0 ONE-O- 403E 20.1 p-Benzoylacetamidobenzoic acid.

5 the invention, but it is to be understood that the invention is notlimited thereto:

OCOCHZGONHOOOOH i. e., sodium sulfite, and the like. If desired theremay also be present in thedeveloper a coupling 7-b n y ph hoxyaceticacid. aid injthe form of an inorganic or organic base 00112-000151 suchas pyridine, quinoline, or ammonium hydroxide. v Q0 0 oHzoo-NHThe-following exampes will serve to illustrate 22.2-p-benzoylacetamidobenzamido-6 stearoyl- Example Iamino-p-toluenesulfonic acid- A photographic silver bromide emulsioncon- CHQ NHCOCwHsfi taining per kilo of emulsion .5 part of 3-stearoy1-amino-5-sulfo-acetoacetanilide as the color O O formeris exposed, thelatent image developed in a Metol-I-Iydr'oquinone Developer, re-exposedTere hthaloylbisa etanilide and the residual silver halide developed for10 24. 4.4methy1enebisacetoacetanilide, minutes in a solution of thefollowing composition: omooomoorrn-O-omQ-vnoo0112000113 V 7 p Potassiumcarbonate grams 20 25. p-Sulfamylbenzoylacetanlllde. sodium COCHzCONHC-SO:NH2 w Ethylene diamine 30 4-(p-hydroxyethylamino) 6 phenylami- 26.N,N-l-methylethylenebisaceto-acetamide H no-metam'lic acid grams 3onaooc1120oNHoH oHz-NHoooH2o0oH3 f 1000 H, V The developed silver imagesare bleached with 27. 2.4-pentanedione 55 potassium ferricyanide andfixed in an acid CHdCOCHzCOCHS hardening hypo solution. There is thusobtained a yellow dyestufi" image which is stable to acids and alkalioxidizing agents. No difficulty is inlgegfgygggggfiggile. volved inefiecting removal of the developer from y the emulsion by the usualwashing procedure.

CNCHzCO-NH-O V Example II 31. a-Phenylsulfonylacetophenone. Theprocedure is the same as in Example I ex- 32. 2-(pbenzoylacetamidophenyl)-1octadecylcepting that the4-(p-hydroxyethylamino) -6- 5-benzimidazolesu1fonic acid. .75phenylamino-metanilic acid is replaced by 4-(5- 28.1.3-diphenyl-1.3-propanedione.

A photographic silver "bromide emulsion is exposed and color developedin a developer having the following composition:

After bleaching with rerricyanide bleach and 'iixing in an'acidhardening fixer, there is obtained a magenta azine dye "image. Nostaining is observed, nor is any diiliculty met with in the completeremoval or the developer from the emulsion by the usual water washing.

Example IV The procedure 'is the same as "in Example III excepting that'the B-hydroxyquinoline is replaced by the ethyl urethane of phenyl J-acid. 'By working up the emulsion as in Example III a cyan azine dye"image isobtained.

Example V photographic silver halide emulsion carrying a silver 'halideimage was developed for 15 minutes in ar developer of the -followingcomposition:

fi-phenylamino 4 .(p hydroxyethylamino) -metanilic acid grams 4Benzoylacet-2maphthylamine "5 sulronamide "grams" 3 Sodium sulfite do 60Potassium carbonate do 20 Ethylene diamine d0 30 Water to cc 1000 Thefilm, after washing, was bleached in ferricyanide-bleach and fixed inacid hardening hypo. There was directly obtained a yellow dye image, noalkaline treatment being necessary.

Example VJ An integral tripack \having as the bottom layer a redsensitive emulsion containing as a cyan color former6-(4octadetsoxyphenylaniino? -'1- naphthOl-S-Sulfonicacid of theformula:

CpHyO-O-NH -so,H

as the middle layer a green sensitive emulsion containing as themagenta'color former 2-stearoylamino 6 (8 hydroxycinchoninylamino)-toluenei-sulfonie acid acid of the formula:

| CONH NC 0 CnHas SOaH and as the outermost layer a blue sensitiveemulsion containing as the yellow color former 2(benzoylacetamidophenyl) 1 octa'decyl 5- benz'imidazole sulfonic acidwas exposed, developed in black and white, re-exposed and the residualsilver halide developed for 12 minutes in a developer of the followingcomposition:

G-phenylamino --4 (,6, hydroxyethylam'ino) -metanilic acid grams 8Potassium carbonate do 20 sodium sulfite do 60 Potassium bromide do 10Benzylamine do 5 Water to cc 1000 The film after development is washed,bleached in ferricyanide bleach, and fixed in an acid hardening hypo.There was thus obtained a positive dyestufi image in each of the three1ayers-a cyan dye image in the bottom layer, a magenta dye image in themiddle layer, and a brilliant yellow dye image in the top layer.

Similar results are obtained by replacing the metanilic acid derivativesof the above examples by other developers listed hereinabove.

Various modifications of the invention will occur to operators in thisfield, and I accordingly do not intend to be limited in the patentgranted except 'as necessitated by the appended claims.

I claim:

1. A photographic developer comprising an alkaline aqueous :solution ofan alkali metal sulfite and .a compound selected rrom the class of thefollowing constitution:

and

NHR:

wherein R is selected from .the class consisting of hydrogen and alkyl,R1 is selected from the class consisting of alkyl, carboxyalkyl,hydroxyalkyl, aryl, carboxyalkylaryl, carboxyalkoxyaryl,hydroxyalkylaryl and hydroxyalkoxyaryl, R2 is an alkyl group substitutedby a hydroxyl roup, X and Y are selected from the class consisting ofhydrogen, alkyl, sulfo and carboxy, and Z; represents the atomsnecessary to complete a G-membered isocyclic ring.

2. The composition as defined in claim 1 wherein Y is hydrogen and X issulfo.

3. A photographic developer as defined in claim 1 wherein Y is hydrogenand X is sulfo and wherein the developer contains a color former capableof reacting with the oxidation products of a primary aromatic aminodeveloper to form a dye image.

4. A photographic developer for producing azine dyestuff images on colordevelopment comprising aqueous alkaline solution of a color formercapable of reacting with the oxidation products of a primary aromaticamino developer to form a dye image and4-(fl-hydroxyethylamino)-6-pheny1- aminometanilic acid.

5. The composition as defined in claim 4 wherein the color former isS-hydroxyquinoline.

and

wherein R'is selected from the class consistin of hydrogen and alkyl, R1is selected from the class consisting of alkyl, carboxyalkyl,hydroxyalkyl, aryl, carboxyalkylaryl, carboxyalkoxyaryl,hydroxyalkylaryl and hydroxyalkoxyaryl, R2 is an alkyl group substitutedby a hydroxyl group, X and Y are selected from the class consisting ofhydrogen, alkyl, sulfo and carboxy, and Z represents the atoms necessaryto complete a G-membered isocyclic ring.

'7. The process as defined in. claim 6 wherein Y is hydrogen and X issulfo.

8. The process of directlyproducing yellow dye images resistant tosplitting by strong mineral acids which comprises developing adevelopable silver halide emulsion in the presence of an open chain ketomethylene compound with a photographic developer containing as theactive developing agent a compound of the following formula:

NR-R

r a Y 2 3 4 NH-Rz azine dyestuff images on color developmentcomand NH: 7or wherein R is selected from the class consisting of hydrogen andalkyl, R1 is selected from the class of alkyl, carboxyalkyl,hydroxyallsylraryl; carboxyalkylaryl, carboxyalkoxyaryl,'hydroxyalkylaryL'hydroxyalkoxyaryl, Rz'is an alkyl group substituted bya hydroxyl group, X and Y are selected from the class consisting ofhydrogen, alkyl, sulfo and carboxy, and Z represents the atomsnecesbenzoylacet' radical with a 4.6 diamino'metanilic acid in which thenitrogen atom in the-G-position is substituted by aryl and the nitrogenatom in the 4-position by hydroxy alkyl.

12. The process as definedin claim 11 wherein the 4.6-diaminometanilicacid is fi-phenylamino- 4 (fl-hydroxyethylaminoi metam'lic acid. y

13. A photographic developer for producing prising an aqueous alkalinesolutionof 4- (/3-;hy droxyethylamino) -6-phenylaminometaniiic, P acid,

and an alkali metal sulfite:

, RTGI fr Ea 7 REFERENCES-CITED H The following references are of;record in the file ofthis'patent: T TES P T NTS UNITED Number Name Date2,304,953 Peterson Dec. 15, 1942 2,489,440 Schmidt et a1. NOV. 1, 1949FOREIGN PATENTS. '1 Number Country Date {$3,064 Great Britain May 6,1943

1. A PHOTOGRAPHIC DEVELOPER COMPRISING AN ALKALINE AQUEOUS SOLUTION OFAN ALKALINE METAL SULFITE AND A COMPOUND SELECTED FROM THE CLASS OF THEFOLLOWING CONSTITUTION: